TWI609030B - Polymer, organic layer composition, and method of forming patterns - Google Patents

Description

Polymer, organic layer composition and method of forming a pattern

The present invention discloses a novel polymer, an organic layer composition comprising the polymer, and a method of forming a pattern using the organic layer composition.

Recently, highly integrated designs based on reduced size (miniaturization) and complexity of electronic devices have accelerated the development of more advanced materials and related processes, and therefore, the use of conventional photoresist lithography also requires new patterned materials. And technology. In a patterning process, an organic layer, referred to as a hard mask layer, can be formed as a hard interlayer to transfer the fine pattern of photoresist down to a sufficient depth on the substrate without collapse of the substrate. The hard mask layer acts as an interlayer to transfer the fine pattern of photoresist to the material layer by a selective etching process. Therefore, the hard mask layer requires features such as etch resistance to withstand multiple etching processes. On the other hand, a spin coating method has recently been proposed instead of a chemical vapor deposition (CVD) method to form a hard mask layer. In general, since the heat resistance and the etching resistance have a trade-off relationship with the rotation characteristics, an organic layer material satisfying all the characteristics is required.

An embodiment provides a polymer having satisfactory heat resistance and etching resistance while ensuring solubility in a solvent, gap filling characteristics, and planarization characteristics.

Another embodiment provides an organic layer composition comprising the polymer.

Yet another embodiment provides a method of forming a pattern using the organic layer composition.

According to an embodiment, a polymer comprises the structural unit represented by Chemical Formula 1. [Chemical Formula 1]

In Chemical Formula 1, Ar ¹ and Ar ^{2 are} independently a substituted or unsubstituted benzene ring or an aromatic ring containing two to four fused substituted or unsubstituted benzene rings, A ¹ and A ² Independently a substituted or unsubstituted aromatic ring, the limitation is that at least one of A ¹ and A ² is substituted with a hydrogen-bondable functional group, and the number of said hydrogen-bondable functional groups of A ¹ The sum of the amounts of the hydrogen bondable functional groups with A ² is greater than or equal to 3, L is a divalent organic group, and * is a point of attachment.

The hydrogen bondable functional group can be a hydroxyl group, an amine, or a combination thereof.

The A ¹ and the A ² may independently be a substituted or unsubstituted aromatic ring group selected from Group 1. [Group 1]

In the group 1, the connection point is not particularly limited.

The L may be represented by one of Chemical Formula Z1 to Chemical Formula Z4. [Chemical Formula Z1] [Chemical Formula Z2] [Chemical Formula Z3] [Chemical Formula Z4]

In the chemical formula Z1 to the chemical formula Z4, a and b are independently 0 or 1, c is an integer of 1 to 5, and Y ¹ to Y ^{4 are} independently selected from the substituted or unsubstituted portion of Group 2. One, and * is the connection point: [Group 2]

In group 2, M, M' and M'' are independently substituted or unsubstituted C1 to C10 alkyl, O, S, SO ₂ , CR ^a R ^b , NR ^c or carbonyl, wherein R ^a , R ^b and R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen atom, halogen containing group or a combination thereof, r is an integer from 0 to 10, and s is an integer from 3 to 10.

The sum of the number of hydrogen-bondable functional groups of A ^{1 and the number} of hydrogen-bondable functional groups of A ² is greater than or equal to 3 and less than or equal to 6.

The structural unit represented by Chemical Formula 1 can be represented by one of Chemical Formula 1-1 and Chemical Formula 1-2. [Chemical Formula 1-1] [Chemical Formula 1-2]

In Chemical Formula 1-1 and Chemical Formula 1-2, R ¹ to R ^{6 are} independently a hydroxyl group, an amine or a combination thereof, and n ¹ to n ^{6 are} independently an integer of 0 to 3, a sum of n ¹ and n ² and n ^The sum of ³ to n ⁶ is independently greater than or equal to 3, and Z ¹ and Z ^{2 are} independently hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or not Substituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 alkoxy or a combination thereof, k ¹ and k ^{2 are} independently an integer from 0 to 4, L is a divalent organic group, and * is Junction.

The polymer may further contain a structural unit represented by Chemical Formula 2. [Chemical Formula 2]

In Chemical Formula 2, X is an aromatic ring substituted with at least one hydrogen-bondable functional group or a heteroaryl ring group substituted with at least one hydrogen-bondable functional group, L is a divalent organic group, and * is a point of attachment.

In Chemical Formula 2, the hydrogen bondable functional group may be a hydroxyl group, an amine, or a combination thereof.

The polymer can have a weight average molecular weight of from about 500 to about 200,000.

According to another embodiment, an organic layer composition comprising the polymer and a solvent is provided.

According to another embodiment, a method of forming a pattern includes: providing a material layer on a substrate; applying an organic layer composition as described in claim 10 on the material layer; and performing the organic layer composition on the material layer Heat treatment to provide a hard mask layer; providing a thin layer containing germanium on the hard mask layer; providing a photoresist layer on the thin layer containing germanium; exposing and developing the photoresist layer to Forming a photoresist pattern; selectively using the photoresist pattern to remove the thin layer containing germanium and the hard mask layer to expose a portion of the material layer; and etching the layer of the material layer Exposed part.

The organic layer composition can be applied using a spin coating method.

A bottom antireflective coating (BARC) may be further formed prior to forming the photoresist layer.

The novel polymer has satisfactory solubility characteristics as well as excellent mechanical characteristics, etching resistance and heat resistance, and thus can be applied to a spin coating method.

Exemplary embodiments of the present invention are explained in detail below, and the exemplary embodiments can be easily performed by one of ordinary skill in the related art. However, the invention may be embodied in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

The term 'substituted', as used herein, may be taken to mean a moiety selected from a halogen atom (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azide. Base, fluorenyl, fluorenyl, hydrazino, carbonyl, carbamoyl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 alkyl, C2 To C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C2 to C20 heteroaryl, C3 to C20 Substituents for arylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocycloalkyl, and combinations thereof, are substituted for the hydrogen of the compound.

The term 'hetero' as used herein, when used without a definition, includes one to three heteroatoms selected from the group consisting of N, O, S, and P.

Hereinafter, a polymer according to an embodiment will be explained.

The polymer according to an embodiment contains the structural unit represented by Chemical Formula 1. [Chemical Formula 1]

In Chemical Formula 1, Ar ¹ and Ar ^{2 are} independently a substituted or unsubstituted benzene ring or an aromatic ring containing two to four fused substituted or unsubstituted benzene rings, A ¹ and A ² Independently a substituted or unsubstituted aromatic ring, the limitation is that at least one of A ¹ and A ² is substituted with a hydrogen-bondable functional group, and the number of said hydrogen-bondable functional groups of A ¹ The sum of the amounts of the hydrogen bondable functional groups with A ² is greater than or equal to 3, L is a divalent organic group, and * is a point of attachment.

The polymer contains, in the structural unit, an aromatic ring moiety represented by Ar ¹ , Ar ² , A ¹ and A ² , an alkylene group and a linking group moiety represented by L.

First, the polymer contains an aromatic ring portion represented by Ar ¹ , Ar ² , A ¹ and A ² , and thus produces excellent etching resistance.

In Chemical Formula 1, Ar ¹ and Ar ² are aromatic rings, for example, independently substituted or unsubstituted benzene rings, and in another example, Ar ¹ and Ar ^{2 are} independently two to four fused. Substituted or unsubstituted benzene ring.

For example, Ar ¹ and Ar ² may be represented by one of Chemical Formula A to Chemical Formula D. [Chemical Formula A] [Chemical Formula B] [Chemical Formula C] [Chemical Formula D]

Chemical Formula A to Chemical Formula D are shown by cutting the points at which Ar ¹ and Ar ² in Chemical Formula 1 are bonded to A ¹ and A ² . In Chemical Formula A to Chemical Formula D, the aromatic ring is unsubstituted, but may, for example, be a hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted Substituted by a C6 to C30 aryl group or a substituted or unsubstituted C1 to C30 alkoxy group. Further, Ar ¹ and Ar ² in Chemical Formula ¹ may be various fused ring groups other than the fused ring contained in Chemical Formula B to Chemical Formula D.

In this way, the polymer contains a fluorene backbone in the structural unit, and thus heat resistance and etching resistance can be ensured.

In Chemical Formula 1, A ¹ and A ² represent a substituted or unsubstituted aromatic ring, and may, for example, be selected from Group 1, but are not limited thereto. [Group 1]

The connection point of the ring group selected from Group 1 in the structural unit represented by Chemical Formula 1 is not particularly limited. Further, the hydrogen selected from the ring group of Group 1 may be replaced by a substituent, and herein, the kind and amount of the substituent are not particularly limited.

At least one of A ¹ and A ² may be substituted with a hydrogen-bondable functional group, and the number of hydrogen-bondable functional groups substituted in A ¹ may be bonded to the hydrogen-bondable functional group substituted in A ² The sum of the numbers is greater than or equal to 3.

Herein, the hydrogen bondable functional group indicates all groups which react with other groups and form a hydrogen bond, such as a hydroxyl group or an amine, but are not limited thereto.

The polymer contains greater than or equal to about 3 hydrogen bondable functional groups in A ¹ and A ² of the structural unit, and thus solubility in a solvent can be improved. Further, when the polymer is used as an organic layer material, adhesion of the organic layer to the under layer is enhanced, and thus excellent gap filling characteristics and planarization characteristics can be ensured.

For example, in Chemical Formula 1, as long as the sum of the number of hydrogen bondable functional groups substituted in A ¹ and the number of hydrogen bondable functional groups substituted in A ² is greater than or equal to 3 and less than or Equal to 6, the number of each of the hydrogen bondable functional groups substituted in A ¹ and the hydrogen bondable functional groups substituted in A ² can be controlled.

In Chemical Formula 1, L is a divalent organic group, and may be represented, for example, by one of Chemical Formula Z1 to Chemical Formula Z4, but is not limited thereto. [Chemical Formula Z1] [Chemical Formula Z2] [Chemical Formula Z3] [Chemical Formula Z4]

In the chemical formula Z1 to the chemical formula Z4, a and b are independently 0 or 1, c is an integer of 1 to 5, and Y ¹ to Y ^{4 are} independently selected from the substituted or unsubstituted portion of Group 2. One, and * is the connection point: [Group 2]

In group 2, M, M' and M'' are independently substituted or unsubstituted C1 to C10 alkyl, O, S, SO ₂ , CR ^a R ^b , NR ^c or carbonyl, wherein R ^a , R ^b and R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen atom, halogen containing group or a combination thereof, r is an integer from 0 to 10, and s is an integer from 3 to 10.

The connection point in the case of the structure of Chemical Formula 2 in the case where the ring group is selected from the group 2 is not particularly limited but may be any two connection points. Further, the hydrogen selected from the ring group of Group 2 may be substituted with a substituent, and the kind and amount of the substituent are not particularly limited.

The linker is included in the compound contained in the hard mask composition according to an embodiment, and can increase the flexibility of the polymer. This flexible structure lowers the glass transition temperature (Tg) and thus promotes reflow during the baking process as well as increases the free volume of the polymer and improves solubility, and thus improves gap fill performance and planarization.

The polymer may include a plurality of moieties represented by Chemical Formula 1, and the plurality of moieties may have the same structure or different structures.

For example, the structural unit represented by Chemical Formula 1 may be represented by one of Chemical Formula 1-1 and Chemical Formula 1-2, but is not limited thereto. [Chemical Formula 1-1] [Chemical Formula 1-2]

In Chemical Formula 1-1 and Chemical Formula 1-2, R ¹ to R ^{6 are} independently a hydroxyl group, an amine or a combination thereof, and n ¹ to n ^{6 are} independently an integer of 0 to 3, a sum of n ¹ and n ² and n ^The sum of ³ to n ⁶ is independently greater than or equal to 3, and Z ¹ and Z ^{2 are} independently hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or not Substituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 alkoxy or a combination thereof, k ¹ and k ^{2 are} independently an integer from 0 to 4, L is a divalent organic group, and * is Junction.

The polymer may further contain, for example, a structural unit represented by Chemical Formula 2. [Chemical Formula 2]

In Chemical Formula 2, X is an aromatic ring substituted with at least one hydrogen-bondable functional group or a heteroaryl ring group substituted with at least one hydrogen-bondable functional group, L is a divalent organic group, and * is a point of attachment.

In Chemical Formula 2, the hydrogen bondable functional group and the divalent organic group represented by L are the same as described above. Herein, the aromatic ring group may be represented, for example, by one of the groups 1.

In Chemical Formula 2, X may be, for example, but not limited to, an aromatic ring-containing group substituted with about 2 or more hydroxyl groups or a heteroaryl ring-containing group substituted with about 2 or more hydroxyl groups.

Likewise, the polymer may include a plurality of moieties represented by Chemical Formula 2, and the plurality of moieties may have the same structure or different structures.

For example, the polymer can have a weight average molecular weight of from about 500 to about 200,000. When the polymer has a weight average molecular weight within the range, the organic layer composition comprising the polymer can be optimized by adjusting the amount of carbon and solubility in a solvent (for example, a hard mask composition) ()).

When the polymer is used as an organic layer material, when a step is present in the lower substrate (or film) or when a pattern is formed, not only excellent gap filling characteristics and planarization characteristics are provided, but also a uniform film can be formed. And no pinholes and voids are formed during baking or the thickness distribution is not deteriorated.

According to another embodiment, an organic layer composition comprising the polymer and a solvent is provided.

The solvent may be any one having sufficient solubility or dispersibility for the polymer, and may be, for example, at least one selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, and diethyl ether. Glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, methylpyrrolidone Ethylacetone and ethyl 3-ethoxypropionate.

The polymer may be included in an amount of from about 1% by weight to about 50% by weight based on the total of the organic layer composition. When the polymer is contained within the range, the thickness, surface roughness, and planarization of the organic layer can be controlled.

The organic layer composition may further contain an additive such as a surfactant, a crosslinking agent, a thermal acid generator, a plasticizer or the like.

The surfactant may include, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol or a quaternary ammonium salt, but is not limited thereto.

The crosslinking agent may be, for example, a melamine-based agent, a substituted urea-based agent, or a polymer-based agent. In one embodiment, the crosslinker having at least two crosslinks to form a substituent may be, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated Melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxy Methylated thiourea, or butoxymethylated thiourea, and the like.

The crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound containing a crosslinking substituent containing an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule.

The thermal acid generator may be, for example, an acidic compound or/and 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, or other organic sulfonic acid. The ester compound or the like is not limited thereto, and the acidic compound is, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxyl group. Benzoic acid, naphthyl carbonic acid, and the like.

The additive may be present in an amount of from about 0.001 part by weight to 75 parts by weight based on 100 parts by weight of the organic layer composition.

According to another embodiment, an organic layer fabricated using the organic layer composition is provided. The organic layer may be formed, for example, by coating an organic layer composition on a substrate and heat-treating the organic layer composition to cure, and may include, for example, a hard mask layer for an electronic device, a planarization layer, Sacrificial layer, filler, etc.

Hereinafter, a method of forming a pattern by using the organic layer composition will be described.

A method of forming a pattern according to an embodiment includes: providing a material layer on a substrate; applying the organic layer composition comprising the polymer and the solvent; and the organic layer comprising a monomer and the solvent The composition is heat treated to form a hard mask layer; a thin layer containing germanium is formed on the hard mask layer; a photoresist layer is formed on the thin layer containing germanium; and the photoresist layer is exposed and Developing to form a photoresist pattern; selectively using the photoresist pattern to remove the thin layer containing germanium and the hard mask layer to expose a portion of the material layer; and etching the material The exposed portion of the layer.

The substrate can be, for example, a tantalum wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned, such as a metal layer (such as an aluminum layer and a copper layer), a semiconductor layer (such as a germanium layer), or an insulator layer (such as a hafnium oxide layer and a tantalum nitride layer). The material layer can be formed by a method such as a chemical vapor deposition (CVD) process.

The organic layer composition is the same as described above and can be applied by spin coating in the form of a solution. Herein, the thickness of the organic layer composition is not particularly limited, but may be, for example, about 50 Å to about 100,000 Å.

The heat treatment of the organic layer composition may be performed, for example, at about 100 ° C to about 500 ° C for about 10 seconds to about 1 hour.

The thin layer containing germanium may be formed of, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiO, and/or SiN.

The method may further include forming a bottom anti-reflective coating (BARC) prior to forming the photoresist layer on the thin layer containing germanium.

Exposure to the photoresist layer can be performed using, for example, ArF, KrF, or EUV. After the exposure, the heat treatment may be performed at about 100 ° C to about 500 ° C.

The etching process of the exposed portion of the material layer may be performed by a dry etching process using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl _{3 ,} and a mixed gas thereof. But not limited.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, or the like, such as a variety of patterns of the semiconductor integrated circuit device.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are exemplary, and the invention is not limited thereto.

Synthesis example

Synthesis Example 1 38 g of 4,4'-(9H-fluorene-9,9-diyl)diphenyl-1,2-diol, 17 g of 1,4-bis(methoxymethyl)benzene, 82 g propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of diethyl sulfate were placed in a flask and stirred at 100 ° C to carry out a polymerization reaction. When the weight average molecular weight reaches 2,000 to 3,500, the reaction is terminated. When the polymerization was completed, the reactant was slowly cooled to room temperature, and then added to 40 g of distilled water and 400 g of methanol, and the mixture was vigorously stirred and then allowed to stand. After removing the supernatant therefrom, the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was vigorously stirred by using 320 g of methanol and 320 g of water, and then allowed to stand still. Set (primary). Herein, after removing the supernatant obtained therefrom, the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (secondary). The primary and secondary processes were then considered a purification process that was repeated a total of three times. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer comprising the structural unit represented by Chemical Formula 1a ( Mw: 3,500). [Chemical Formula 1a]

Synthesis Example 2 by using 48 g of 6,6'-(9H-fluoren-9,9-diyl)dinaphthyl-1,2-diol, 17 g of 1,3-bis(methoxymethyl)benzene 98 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.5 g of diethyl sulfate and a polymer (Mw: 3,500) containing the structural unit represented by Chemical Formula 1b was obtained by the same synthesis as in Synthesis Example 1. [Chemical Formula 1b]

Synthesis Example 3 by using 23 g of hydrazine-1,6-diol, 34 g of 1,4-bis(methoxymethyl)benzene, 38 g of 4,4'-(9H-芴-9,9-di Diphenyl-1,2-diol, 143 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.7 g of diethyl sulfate and obtained by the same synthesis as in Synthesis Example 1 to obtain a structure represented by Chemical Formula 1c The polymer of the unit (Mw: 3,200). [Chemical Formula 1c]

Synthesis Example 4 by using 38 g of 4,4'-(9H-fluoren-9,9-diyl)diphenyl-1,2-diol, 47 g of 4,4'-(propane-2,2-di Bis()-(4-(methoxymethyl)phenoxy)benzene), 128 g propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g diethyl sulfate and synthesized by the same synthesis as in Synthesis Example 1. A polymer (Mw: 3,500) containing the structural unit represented by Chemical Formula 1d was obtained. [Chemical Formula 1d]

Synthesis Example 5 by using 41 g of 5,5'-(9H-fluorene-9,9-diyl)diphenyl-1,2,3-triol, 47 g of 4,4'-oxybis ((A) Oxymethyl)benzene), 133 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.5 g of diethyl sulfate and the same synthesis as in Synthesis Example 1 was carried out to obtain a polymer comprising the structural unit represented by Chemical Formula 1e ( Mw: 3,100). [Chemical Formula 1e]

Synthesis Example 6 by using 41 g of 5,5'-(9H-fluorene-9,9-diyl)diphenyl-1,2,3-triol, 36 g of 1,6-bis (4-(methoxy) Methyl)phenoxy)hexane, 116 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.5 g of diethyl sulfate and obtained by the same synthesis as in Synthesis Example 1 to obtain a structural unit represented by Chemical Formula 1f Polymer (Mw: 3,200). [Chemical Formula 1f]

Synthesis Example 7 by using 20 g of 5,5'-(9H-fluorene-9,9-diyl)diphenyl-1,2,3-triol, 17 g of 1,3-bis(methoxymethyl) Benzene, 7 g of 1H-indol-5-ol, 103 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.5 g of diethyl sulfate and obtained by the same synthesis as in Synthesis Example 1 containing the formula represented by Chemical Formula 1g Polymer of structural unit (Mw: 3,000). [Chemical Formula 1g]

Synthesis Example 8 by using 20 g of 5,5'-(9H-fluorene-9,9-diyl)diphenyl-1,2,3-triol, 26 g of 4,4'-oxybis ((A) Oxymethyl)benzene), 6 g of 1H-indole, 123 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.5 g of diethyl sulfate and obtained by the same synthesis as in Synthesis Example 1 are represented by the chemical formula 1h The polymer of the structural unit (Mw: 3,500). [Chemical Formula 1h]

Synthesis Example 9 by using 48 g of 6,6'-(9H-fluoren-9,9-diyl)dinaphthyl-1,2-diol, 12 g of 4-hydroxybenzaldehyde, and 141 g of propylene glycol monomethyl ether The acid ester (PGMEA) and 0.3 g of diethyl sulfate were passed through the same synthesis as in Synthesis Example 1 to obtain a polymer (Mw: 3,500) containing the structural unit represented by Chemical Formula 1i. [Chemical Formula 1i]

Synthesis Example 10 by using 38 g of 4,4'-(9H-fluorene-9,9-diyl)diphenyl-1,2-diol, 17 g of 4-hydroxy-1-naphthaldehyde, and 129 g of propylene glycol Methyl ether acetate (PGMEA) and 0.3 g of diethyl sulfate were passed through the same synthesis as in Synthesis Example 1 to obtain a polymer (Mw: 3,200) containing the structural unit represented by Chemical Formula 1j. [Chemical Formula 1j]

Synthesis Example 11 by using 19 g of 4,4'-(9H-fluorene-9,9-diyl)diphenyl-1,2-diol, 17 g of 2-hydroxy-1-naphthaldehyde, and 7 g of naphthalene- 1-alcohol, 91 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.3 g of p-toluenesulfonic acid hydrate and the same synthesis as in Synthesis Example 1 was carried out to obtain a polymer comprising the structural unit represented by Chemical Formula 1k (Mw: 3,000). [Chemical Formula 1k]

Synthesis Example 12 by using 19 g of 4,4'-(9H-fluorene-9,9-diyl)diphenyl-1,2-diol, 26 g of 4,4'-oxybis((methoxy) Methyl)benzene), 7 g of naphthyl-2-ol, 122 g of propylene glycol monomethyl ether acetate (PGMEA) and 0.5 g of diethyl sulfate and obtained by the same synthesis as in Synthesis Example 1 containing the formula represented by Chemical Formula 1l Polymer of structural unit (Mw: 3, 100). [Chemical Formula 1l]

Comparative Synthesis Example 1 23 g of benzopyrene, 17 g of 1,4-bis(methoxymethyl)benzene, 60 g of propylene glycol monomethyl ether acetate (PGMEA) and 1.23 g of diethyl sulfate at 100 ° C The polymerization was carried out by stirring for 2 hours to 24 hours. When the weight average molecular weight reaches the range of 2,000 to 3,500, the reaction is terminated. When the polymerization was completed, the reaction was slowly cooled to room temperature, added to 40 g of distilled water and 400 g of methanol, and the mixture was vigorously stirred and then allowed to stand. After the supernatant was removed therefrom, the precipitate therein was dissolved in 80 g of cyclohexanone, and the solution was vigorously stirred by using 320 g of methanol, and then allowed to stand (primary). Herein, after the supernatant obtained therefrom was removed again, the precipitate therein was dissolved in 80 g of cyclohexanone (secondary). A polymer (Mw: 2, 700) containing the structural unit represented by Chemical Formula X was obtained by the same synthesis as in Synthesis Example 1. [Chemical Formula X]

Comparative Synthesis Example 2 by using 45 g of 6,6'-(9H-fluoren-9,9-diyl)dinaphthyl-2-ol, 17 g of 1,4-bis(methoxymethyl)benzene, 62 g propylene glycol monomethyl ether acetate (PGMEA) and 0.6 g of diethyl sulfate and a polymer represented by the chemical formula Y (Mw: 3,500) was obtained by the same synthesis as in Synthesis Example 1. [Chemical Formula Y]

Preparation of hard mask composition

Example 1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) cyclohexanone polymer according to Synthesis Example 1: a mixed solvent (7 3 (v / v) ) in, and the solution was filtered to prepare a hard coat Curtain composition. The polymer compound is contained in an amount of from 1 wt% to 20 wt%, based on the total thickness of the hard mask composition, depending on the desired thickness.

Example 2 to Example 12 Each of the hard mask compositions was prepared in the same manner as in Example 1 except that the polymers of Synthesis Example 2 to Synthesis Example 12 were used instead of the polymer of Synthesis Example 1, respectively.

In Comparative Example 1 and Comparative Example 2 , a hard mask composition was prepared in the same manner as in Example 1 except that the polymer according to Comparative Synthesis Example 1 and Comparative Synthesis Example 2 was used instead of the polymer according to Synthesis Example 1.

Evaluation of Gap Filling Features Each of the hard mask compositions according to Examples 1 to 12 and Comparative Examples 1 and 2 was spin-coated on a germanium wafer having a hole pattern to form a thin film, and by using V-SEM The device checks the cross section of the film. The amount of compound in the hard mask composition was adjusted to form a 2,000 Å thick film on the bare wafer.

The results are shown in Table 1. [Table 1]

Referring to Table 1, each of the films formed from the hard mask compositions according to Examples 1 to 12, respectively, exhibited no voids, and thus exhibited excellent gap filling characteristics.

Evaluation of the planarization feature Each of the hard mask compositions according to Examples 1 to 5, Example 7, Example 8, Example 11, and Example 12 and Comparative Example 1 and Comparative Example 2 was spin-coated on a germanium wafer having a hole pattern. The film was baked at 400 ° C to form a film, respectively, and the cross section of the film was examined by using a V-SEM apparatus. The amount of compound in the hard mask composition was adjusted to form a 1,400 Å thick film on the bare wafer.

The planarization characteristics were evaluated by measuring the thickness differences h ₁ , h ₂ , h ₃ , h ₄ , h ₅ , h _{6 of the} resist underlayer in the regions having pores and the regions without pores. The flattening feature is digitized according to Equation 1. As the film thickness difference between the patterned region and the unpatterned region becomes smaller, that is, as the digitized value becomes smaller, the planarization feature can become more excellent. Equation 1

The results are shown in Table 2. [Table 2]

Referring to Table 2, the hard masks according to Examples 1 to 5, Example 7, Example 8, Example 11, and Example 12, respectively, were compared with the films formed by the hard mask compositions according to Comparative Example 1 and Comparative Example 2, respectively. The film formed by the curtain composition exhibits excellent planarization.

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not limited to the disclosed embodiments, but instead, is intended to cover the spirit and scope of the appended claims. Various finishes and equivalent configurations within range.

h ₁ , h ₂ , h ₃ , h ₄ , h ₅ , h ₆ ‧ ‧ thickness difference

FIG. 1 is a reference diagram for explaining a calculation equation 1 for evaluating a flattening feature.

h ₁ , h ₂ , h ₃ , h ₄ , h ₅ , h ₆ ‧ ‧ thickness difference

Claims (18)

A polymer comprising the structural unit represented by Chemical Formula 1: Wherein, in Chemical Formula 1, Ar ¹ and Ar ^{2 are} independently a substituted or unsubstituted benzene ring or an aromatic ring containing two to four fused substituted or unsubstituted benzene rings, A ¹ and A ^{2 is} independently a substituted or unsubstituted aromatic ring, with the proviso that at least one of A ¹ and A ² is substituted with a hydrogen-bondable functional group, and the number of hydrogen-bondable functional groups of A ¹ The sum of the number of hydrogen-bondable functional groups with A ² is greater than or equal to 3, L is a divalent organic group, and * is a point of attachment, wherein the L is represented by one of the chemical formula Z1 to the chemical formula Z3: Wherein, in the chemical formula Z1 to the chemical formula Z3, a and b are independently 0 or 1, and Y ¹ to Y ^{4 are} independently one selected from the substituted or unsubstituted portions of the group 2, and * is Junction: Wherein, in Group 2, M, M' and M" are independently substituted or unsubstituted C1 to C10 alkyl, O, S, SO ₂ , CR ^a R ^b , NR ^c or carbonyl, wherein R ^a , R ^b and R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen atom, halogen-containing group or a combination thereof, r is an integer from 0 to 10, and s is an integer from 3 to 10. The polymer of claim 1, wherein the hydrogen bondable functional group is a hydroxyl group, an amine, or a combination thereof. The polymer of claim ¹ , wherein the A ¹ and the A ^{2 are} independently a substituted or unsubstituted aromatic ring selected from the group consisting of: Among them, in the group 1, the connection point is not particularly limited. The polymer of claim ¹ , wherein the sum of the number of the hydrogen bondable functional groups of A ^{1 and the number} of the hydrogen bondable functional groups of A ² is greater than or equal to 3 and less than or Equal to 6. The polymer according to claim 1, wherein the structural unit represented by Chemical Formula 1 is represented by one of Chemical Formula 1-1 and Chemical Formula 1-2: [Chemical Formula 1-1] Wherein, in Chemical Formula 1-1 and Chemical Formula 1-2, R ¹ to R ^{6 are} independently a hydroxyl group, an amine or a combination thereof, and n ¹ to n ^{6 are} independently an integer of 0 to 3, and the sum of n ¹ and n ² And the sum of n ³ to n ⁶ is independently greater than or equal to 3, and Z ¹ and Z ^{2 are} independently hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group or a combination thereof, k ¹ and k ^{2 are} independently an integer of 0 to 4, and L is a divalent organic group, and * is the connection point. The polymer according to claim 1, wherein the polymer further comprises a structural unit represented by Chemical Formula 2: [Chemical Formula 2] *-XL-* wherein, in Chemical Formula 2, X is an aromatic ring substituted with at least one hydrogen-bondable functional group or a heteroaryl ring group substituted with at least one hydrogen-bondable functional group, and L is a divalent organic group And * is the connection point. The polymer of claim 6, wherein the hydrogen bondable functional group is a hydroxyl group, an amine, or a combination thereof. The polymer of claim 1, wherein the polymer has a weight average molecular weight of from 500 to 200,000. An organic layer composition comprising a polymer containing a structural unit represented by Chemical Formula 1 and a solvent, Wherein, in Chemical Formula 1, Ar ¹ and Ar ^{2 are} independently a substituted or unsubstituted benzene ring or an aromatic ring containing two to four fused substituted or unsubstituted benzene rings, A ¹ and A ^{2 is} independently a substituted or unsubstituted aromatic ring, with the proviso that at least one of A ¹ and A ² is substituted with a hydrogen-bondable functional group, and the number of hydrogen-bondable functional groups of A ¹ The sum of the number of hydrogen-bondable functional groups with A ² is greater than or equal to 3, L is a divalent organic group, and * is a point of attachment, wherein the L is represented by one of the chemical formula Z1 to the chemical formula Z3: Wherein, in the chemical formula Z1 to the chemical formula Z3, a and b are independently 0 or 1, and Y ¹ to Y ^{4 are} independently one selected from the substituted or unsubstituted portions of the group 2, and * is Connection point: [Group 2] Wherein, in Group 2, M, M' and M" are independently substituted or unsubstituted C1 to C10 alkyl, O, S, SO ₂ , CR ^a R ^b , NR ^c or carbonyl, wherein R ^a , R ^b and R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen atom, halogen-containing group or a combination thereof, r is an integer from 0 to 10, and s is an integer from 3 to 10. The organic layer composition of claim 9, wherein the hydrogen bondable functional group is a hydroxyl group, an amine or a combination thereof. The organic layer composition of claim 9, wherein the A ¹ and the A ^{2 are} independently a substituted or unsubstituted aromatic ring group selected from the group 1: Among them, in the group 1, the connection point is not particularly limited. The organic layer composition of claim 9, wherein the number of the hydrogen bondable functional groups substituted in A ¹ is the same as the hydrogen bondable functional group substituted in A ² The sum of the numbers is greater than or equal to 3 and less than or equal to 6. The organic layer composition according to claim 9, wherein the structural unit represented by Chemical Formula 1 is represented by one of Chemical Formula 1-1 and Chemical Formula 1-2: [Chemical Formula 1-2] Wherein, in Chemical Formula 1-1 and Chemical Formula 1-2, R ¹ to R ^{6 are} independently a hydroxyl group, an amine or a combination thereof, and n ¹ to n ^{6 are} independently an integer of 0 to 3, and the sum of n ¹ and n ² And the sum of n ³ to n ⁶ is independently greater than or equal to 3, and Z ¹ and Z ^{2 are} independently hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group or a combination thereof, k ¹ and k ^{2 are} independently an integer of 0 to 4, and L is a divalent organic group, and * is the connection point. The organic layer composition according to claim 9, wherein the polymer further comprises a structural unit represented by Chemical Formula 2: [Chemical Formula 2] *-XL-* wherein, in Chemical Formula 2, X is at least a hydrogen-bondable functional group-substituted aromatic ring or a heteroaryl ring group substituted with at least one hydrogen-bondable functional group, L is a divalent organic group, and * is the connection point. The organic layer composition of claim 14, wherein the hydrogen bondable functional group is a hydroxyl group, an amine, or a combination thereof. The organic layer composition of claim 9, wherein the polymer has a weight average molecular weight of 500 to 200,000. A method of forming a pattern, comprising: providing a material layer on a substrate, and applying an organic layer composition according to any one of claims 9 to 16 on the material layer, The organic layer composition is heat-treated to provide a hard mask layer, a thin layer containing germanium is disposed on the hard mask layer, and a photoresist layer is disposed on the thin layer containing germanium, and the photoresist layer is disposed on the photoresist layer Exposing and developing to form a photoresist pattern, the photoresist pattern is used to selectively remove the thin layer containing germanium and the hard mask layer to expose a portion of the material layer, and an etching station The exposed portion of the layer of material. The method of forming a pattern according to claim 17, wherein the organic layer composition is applied using a spin coating method.